CN106906363B - A kind of treatment method of arsenic-containing copper slag - Google Patents
A kind of treatment method of arsenic-containing copper slag Download PDFInfo
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- CN106906363B CN106906363B CN201710038220.7A CN201710038220A CN106906363B CN 106906363 B CN106906363 B CN 106906363B CN 201710038220 A CN201710038220 A CN 201710038220A CN 106906363 B CN106906363 B CN 106906363B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
本发明涉及一种含砷铜渣的处理方法，属于湿法冶金技术领域。本发明针对铜的质量百分数含量为10~70%、砷的质量百分数含量为5~20%、铁的质量百分数含量为5~30%的含砷铜渣提出的处理方法，在含砷铜渣中加入稀硫酸，搅拌均匀形成矿浆；在矿浆中加入氧化介质反应至矿浆的pH值为1~3，沉淀、固液分离即得到富含铜浸出液和砷铁渣。本发明方法同步实现铜、锌及铟等有价金属浸出至溶液和将砷和铁形成稳定的砷铁固化渣，具有实现有价金属回收率高、工艺流程简单、处理过程清洁高效等特点。The invention relates to a method for treating arsenic-containing copper slag, which belongs to the technical field of hydrometallurgy. The present invention proposes a treatment method for the arsenic-containing copper slag with the mass percentage content of copper being 10-70%, the mass percentage content of arsenic being 5-20%, and the mass percentage content of iron being 5-30%. Add dilute sulfuric acid to the ore slurry, stir evenly to form ore slurry; add an oxidizing medium to the ore slurry to react until the pH value of the ore slurry is 1~3, and precipitate and solid-liquid separation to obtain a copper-rich leaching solution and arsenic-iron slag. The method of the invention simultaneously realizes the leaching of valuable metals such as copper, zinc and indium into the solution and forms arsenic and iron into stable arsenic-iron solidified slag.
Description
Technical field
The present invention relates to a kind of processing methods of slag containing arsenical copper, belong to technical field of wet metallurgy.
Background technique
The more considerable copper of quantity is usually associated in zinc concentrate, especially the content of copper can reach 1% in complicated marmatite
More than, there is higher economic value.In Zinc Hydrometallurgy Process, in leaching or middle leaching-weak-acid leaching technique can only recycle 40 ~
50% metallic copper, remaining is then stayed in leached mud, and copper almost all enters kiln when handling leached mud using rotary kiln evaporation method
Slag, it is difficult to recycle；When handling leached mud using hot acid leaching-out technique, copper enters hot acid leachate with zinc, iron, indium；Using pressurization
When extract technology handles zinc concentrate, copper equally enters oxygen leaching liquid with zinc, iron, indium, most of for above-mentioned two classes leachate
Smelting enterprise recycles copper using solvent extraction and indium-oxidation neutralizes heavy iron or the heavy indium-removing iron by oxidation of neutralization.In leachate point
From in deferrization process, in order to avoid the valuable metals such as heavy iron process zinc, indium, copper enter scum, it usually needs first will be in leachate
Fe3+It is reduced to Fe2+.Currently used method is in acid condition, to utilize the trivalent in zinc sulfide concentrates reducing leaching liquid
Iron ion, but since concentrate utilization rate is low, excessive addition zinc concentrate is needed, the copper easily led in hot acid leachate generates cuprous sulfide
Precipitating enters in slag, and copper, Zn content are high in slag.After reduction liquid using neutralisation sink indium when part copper enter heavy indium slag, need to be in indium
The technical process of slag recovery indium carries out special copper and indium separating treatment, and process flow is relatively complicated, and the rate of recovery is lower；Solvent extraction
It is able to achieve higher copper recovery though following the example of, since leaching liquid measure is big, copper concentration is low, required extraction system is huge, causes big
Amount organic reagent enters in leachate, need to carry out special deoiling treatment.Therefore, the copper of zinc concentrate association for a long time fails to obtain
It preferably recycles, to reduce the comprehensive utilization ratio of resource, causes the waste of resource.
For solve the problems, such as zinc in zinc concentrate smelting process, iron, indium, copper efficiently separate and synthetical recovery, improve metal
The rate of recovery and comprehensive resource utilization rate, the present inventor are public in patent CN201310308061 and CN201410049421
Raising copper recovery method in Zinc Hydrometallurgy Process has been opened, using a kind of slag containing arsenical copper of iron replacement method output, has been realized strong
Effective removing of the high efficiente callback of copper and arsenic in acid solution, and process is generated without arsenic hydride, slag containing arsenical copper can be recycled further
Copper.
Patent of invention CN201410739063.9 discloses a kind of method for recycling copper from copper fumes, solidifying arsenic, side
Method is characterized in that copper fumes progress normal pressure acidleach is first obtained pickle liquor, then carries out oxygen sink arsenic to pickle liquor and obtain scorodite and sink
Contain copper liquid after arsenic.This method preferably realizes the separation of copper and arsenic in infusion solution, but leaching process copper arsenic leaching rate compared with
Low, copper arsenic content is high in leached mud, causes copper resource waste and arsenic pollution.
Currently available technology can complete copper in slag containing arsenical copper, arsenic separation, but process flow is long, process is difficult to control,
Separative efficiency is lower.
Summary of the invention
In view of the problems of the existing technology the present invention, provides a kind of processing method of slag containing arsenical copper, realize valuable metal
High-recovery, process flow be simple, treatment process clean and effective；The spy of characteristic and arsenic, iron precipitating that the present invention is leached for copper
Property, the leaching of copper and being deposited in same reaction kettle same process for arsenic are completed, the acid generated using arsenic and iron precipitation process
Copper is leached, the sulfuric acid needed for copper leaches is met；Using the acid of copper leached in consumption system, low acid needed for maintaining precipitation reaction
Environment is effectively realized that the leaching of valuable metal in slag containing arsenical copper is synchronous with contamination precipitation and is carried out, reaches and efficiently separate recycling
Purpose.
The technical solution adopted by the present invention is that: pulp is carried out to slag containing arsenical copper using dilute sulfuric acid, ore pulp will be formed by and set
In the reaction kettle for having agitating device；It is passed through oxide isolation in reaction kettle, reacts at high temperature, copper and zinc, indium etc. is valuable
Metal is leached to solution, while arsenic and iron are formed stable arsenic iron and solidify slag, obtained after solid-liquor separation solution rich in copper and
Arsenic scum.
A kind of processing method of the slag containing arsenical copper, which is characterized in that specific step is as follows:
(1) ratio for being 20 ~ 100:1 according to the liquid-solid ratio mL:g of dilute sulfuric acid and the slag containing arsenical copper, is added in slag containing arsenical copper
Dilute sulfuric acid stirs evenly to form ore pulp；
(2) it under conditions of 90 ~ 180 DEG C of temperature, is reacted oxide isolation is added in ore pulp obtained by step (1) 2-4 hours
PH value to ore pulp is 1 ~ 3, and precipitating, separation of solid and liquid are obtained rich in copper leachate and arsenic scum, and the main image of arsenic scum is
Innoxious scorodite and bloodstone.
It is 5 ~ 20%, iron that the mass percent content of copper, which is the mass percent content of 10 ~ 70%, arsenic, in the slag containing arsenical copper
Mass percent content be 5 ~ 30%；
Further, the main image of copper is cuprous arsenicization, cuprous oxide one kind or any ratio in the slag containing arsenical copper
Two kinds, the main image of iron is ferrous arsenicization, arsenic iron and/or metallic iron；
The concentration of step (1) dilute sulfuric acid is 10 ~ 30g/L；
Further, dilute sulfuric acid is selected from the heavy ferrous solution or hydrometallurgy of the aqueous solution of industrial sulphuric acid, wet zinc-making system
Electrolyte；
Step (2) oxide isolation is oxygen or air.
The beneficial effects of the present invention are:
(1) present invention slowly aoxidizes slag containing arsenical copper using oxide isolation, dissolves into copper therein, arsenic, iron, zinc, indium etc.
Enter solution；Meanwhile arsenic, iron are precipitated as leached mud in the form of scorodite and bloodstone, thus by copper, zinc, the leaching of indium and arsenic,
Being deposited in same reaction kettle same process for iron is completed, and effectively realizes the leaching process and impurity of valuable metal in slag containing arsenical copper
Precipitation process synchronous carry out；
(2) it is precipitated as bloodstone acidleach copper generated, zinc, indium using iron in reaction process of the invention, ensures leaching
Required sulfuric acid out；Using copper, zinc, indium leach consumption system in acid, maintain precipitation reaction needed for low acid environment, both dropped
Low sour consumption in turn avoids adding neutralizer in the prior art and carrys out the sulfuric acid of neutralization precipitation process generation with maintenance system pH not
Foot, the leaching process and contamination precipitation process free from admixture of valuable metal introduce, and gained copper-containing solution is easily handled, valuable metal
The rate of recovery is high, process flow is simple, clean and effective, energy conservation and environmental protection.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1: the mass percent content of copper is the mass percent of 69.8%, arsenic in the slag containing arsenical copper of the present embodiment
Content is 5.04%, the mass percent content of iron is 5.17%；
A kind of processing method of the slag containing arsenical copper, the specific steps are as follows:
(1) under normal temperature conditions, the ratio for being 100:1 according to the liquid-solid ratio mL:g of dilute sulfuric acid and the slag containing arsenical copper is containing arsenic
Dilute sulfuric acid (dilute sulfuric acid is hydrometallurgical electrolyte, and dilute sulfuric acid concentration is 20g/L) is added in copper ashes, stirs evenly, is starched
Change forms ore pulp；
(2) by pulp conveying obtained by step (1) into the compressive reaction kettle for having agitating device, in 150 DEG C of item of temperature
Under part, oxygen is passed through in the ore pulp in reaction kettle, reacting 3 hours pH value to ore pulp is 1.8, and precipitating, separation of solid and liquid are
It obtains rich in copper leachate and arsenic scum；
After measured, the concentration rich in copper in copper leachate is 6.54g/L, and the mass percent content of arsenic is in arsenic scum
24.6%, the mass percent content of iron is 20.7%；
Copper leaching rate is 98.1% in this example, and the rate of deposition of arsenic is 92.9%, and the rate of deposition of iron is 76.3%.
Embodiment 2: the mass percent content of copper is the mass percent of 35.7%, arsenic in the slag containing arsenical copper of the present embodiment
Content is 9.3%, the mass percent content of iron is 9.7%；
A kind of processing method of the slag containing arsenical copper, the specific steps are as follows:
(1) under normal temperature conditions, the ratio for being 20:1 according to the liquid-solid ratio mL:g of dilute sulfuric acid and the slag containing arsenical copper is containing arsenical copper
Dilute sulfuric acid (dilute sulfuric acid is the heavy ferrous solution of wet zinc-making system, and dilute sulfuric acid concentration is 30g/L) is added in slag, stirs evenly, into
Row pulp forms ore pulp；
(2) by pulp conveying obtained by step (1) into the compressive reaction kettle for having agitating device, in 180 DEG C of item of temperature
Under part, oxygen is passed through in the ore pulp in reaction kettle, reacting 3 hours pH value to ore pulp is 2.97, and precipitating, separation of solid and liquid are
It obtains rich in copper leachate and arsenic scum；
After measured, the concentration rich in copper in copper leachate is 17.1g/L, and the mass percent content of arsenic is in arsenic scum
23.5%, the mass percent content of iron is 29.1%；
Copper leaching rate is 95.7% in this example, and the rate of deposition of arsenic is 92.6%, and the rate of deposition of iron is 99.1%.
Embodiment 3: the mass percent content of copper is the mass percent of 10.1%, arsenic in the slag containing arsenical copper of the present embodiment
Content is 19.8%, the mass percent content of iron is 29.6%；
A kind of processing method of the slag containing arsenical copper, the specific steps are as follows:
(1) under normal temperature conditions, the ratio for being 50:1 according to the liquid-solid ratio mL:g of dilute sulfuric acid and the slag containing arsenical copper is containing arsenical copper
Dilute sulfuric acid (dilute sulfuric acid is the aqueous solution of industrial sulphuric acid, and dilute sulfuric acid concentration is 10g/L) is added in slag, stirs evenly, carries out pulp
Form ore pulp；
(2) by pulp conveying obtained by step (1) into the compressive reaction kettle for having agitating device, in 90 DEG C of condition of temperature
Under, oxygen is passed through in the ore pulp in reaction kettle, reacting 2 hours pH value to ore pulp is 1.02, precipitates, is separated by solid-liquid separation to obtain the final product
To rich in copper leachate and arsenic scum；
After measured, the concentration rich in copper in copper leachate is 2.11g/L, and the mass percent content of arsenic is in arsenic scum
22.1%, the mass percent content of iron is 21.2%；
Copper leaching rate is 99.7% in this example, and the rate of deposition of arsenic is 91.3%, and the rate of deposition of iron is 58.6%.
Claims (2)
1. a kind of processing method of slag containing arsenical copper, which is characterized in that specific step is as follows:
(1) ratio for being 20 ~ 100:1 according to the liquid-solid ratio mL:g of dilute sulfuric acid and the slag containing arsenical copper, is added dilute sulphur in slag containing arsenical copper
Acid stirs evenly to form ore pulp；Wherein the concentration of dilute sulfuric acid is 10 ~ 30g/L；
(2) it under conditions of 90 ~ 180 DEG C of temperature, reacts oxide isolation is added in ore pulp obtained by step (1) to the pH value of ore pulp
It is 1 ~ 3, precipitating, separation of solid and liquid are obtained rich in copper leachate and arsenic scum；The main image of arsenic scum is innoxious smelly green onion
Stone and bloodstone；
It is the matter of 5 ~ 20%, iron that the mass percent content of copper, which is the mass percent content of 10 ~ 70%, arsenic, in the slag containing arsenical copper
Measuring relative content is 5 ~ 30%；
In the slag containing arsenical copper the main image of copper be arsenicization it is cuprous cuprous with the mixture or arsenicization of cuprous oxide, iron it is main
Image is ferrous arsenicization, arsenic iron and/or metallic iron.
2. the processing method of the slag containing arsenical copper according to claim 1, it is characterised in that: step (2) oxide isolation be oxygen or
Air.
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| CN114561547A (en) * | 2022-03-14 | 2022-05-31 | 昆明理工大学 | Method for comprehensively recovering valuable metals in high-zinc copper smelting smoke dust |
| CN116463514B (en) * | 2023-04-19 | 2024-07-19 | 昆明瀚创科技有限公司 | Treatment method of arsenic-containing smoke leaching residues in copper smelting |
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| US4149880A (en) * | 1978-07-19 | 1979-04-17 | Kennecott Copper Corporation | Recovery of copper from arsenic containing metallurgical waste materials |
| CN1358871A (en) * | 2001-11-09 | 2002-07-17 | 北京矿冶研究总院 | Method for extracting copper from copper-containing sulfide minerals |
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2017
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| CN102242268A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for treating black copper slag through electrolytic method |
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| Title |
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| 铜渣生产硫酸铜的试验研究;巫旭;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140715;第13-14、22页 |
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